Ionic liquid-acid aqueous two-phase system

ABSTRACT

Disclosed is a process for extracting or separating metal ions using a composition including: an ionic liquid of formula C + ,-X, in which: C +  is an onium cation including at least one hydrocarbon chain R 1  including from 6 to 20 carbon atoms; X P − is an anion of charge p, the ionic liquid having a solubility in water at 20° C. of at least 10 g/l; an acid; and water. The composition includes two liquid phases: a phase enriched in ionic liquid ϕ IL ; and a phase enriched in water ϕ w , the pH of which is less than or equal to 4.7. The composition is useful for extracting a metal ion from an acidic aqueous medium including a metal ion, for separating metal ions from an aqueous medium including at least two metal ions or for purifying an acidic aqueous solution including a metal ion.

The present invention relates to a composition comprising two liquid phases, one enriched in ionic liquid, the other enriched in acidic aqueous solution, wherein such a composition corresponds to an biphasic ionic-acid liquid aqueous system, and its uses, in particular for extracting metal ions.

Metal ions are generally soluble in acidic, or even strongly acidic, aqueous solutions, and poorly soluble in neutral or basic solutions. Few extraction media are compatible with these acidic conditions.

It is known to use organic solvents, such as kerosene for extracting metal ions from an aqueous acidic phase. These organic solvents are, however, toxic and flammable.

Ionic liquids are increasingly considered as alternative solvents to organic solvents. An ionic liquid is a salt having a melting temperature below 100° C. Ionic liquids are not explosive, and so the risk of explosion or atmospheric pollution is avoided. Ionic liquids are not volatile and have no vapor pressure. The extractant phase therefore remains stable and inert during prolonged storage.

The literature reports the use of hydrophobic ionic liquids that are highly insoluble in water to extract metal ions from aqueous phases. Hydrophobic ionic liquids, however, have the drawback of being generally not only expensive, but also viscous, which makes their handling complex.

In addition, biphasic aqueous systems (ABS) comprising two immiscible aqueous solutions, also make it possible to carry out liquid-liquid extractions without the use of organic or volatile solvents. Most biphasic aqueous systems are based on polymer/salt phases, polymer/polymer phases, or salt/salt phases.

Some biphasic aqueous ionic hydrophilic/inorganic salt systems are known. The appearance of two phases is noted beyond certain concentrations of hydrophilic ionic liquid and inorganic salt, wherein one of the phases consists mainly of ionic liquid and water, while the other consists of inorganic salt and water. The principle underlying the formation of these systems lies in the fact of associating two charged species (ionic liquid and inorganic salt), one being cosmotropic, the other chaotropic, or, in other words, an inorganic salt containing ions. with high hydration-free enthalpy, preferably multivalent ions, and an ionic liquid having a low solvation-free enthalpy, with bulky ions, alkyl chains and/or weakly hydrophilic anions. These systems have so far been mainly developed with a water with a neutral to slightly basic pH (pH<10). They are used for the extraction of organic molecules (food dyes, pharmaceuticals, organic molecules), and more rarely, for the extraction of metal ions: Onghena et al. (Chem Comm 2015, 51, 15932-15935) reports the use of a biphasic aqueous tributyl (tetradecyl) phosphonium chloride system ([P₄₄₄₁₄][Cl])/NaCl for the separation of cobalt ion and nickel ion.

Few biphasic aqueous systems with an acidic aqueous phase have been described so far. However, metal ions are generally soluble in acidic aqueous solutions and poorly soluble in neutral or basic aqueous solution. Aqueous biphasic systems comprising an aqueous acidic phase are therefore particularly sought after.

Ghosh et al. (J. Radioanal. Nucl. Chem., 2014, 302, 925-930) describe the use of a biphasic aqueous system of 1-butyl-3-methylimidazolium chloride [BMIM][Cl]/K₂HPO₄ to extract silver ions. The separation is carried out in a nitric acid medium to avoid precipitating the metals. In this biphasic aqueous system, nitric acid is a spectator salt that does not contribute to phase separation. The medium is quite complex in that many anions are present (Cl⁻, NO₃ ⁻, HPO₄ ⁻), and in that the K⁺ cation is supernumerary, which generates the risk of having a parasitic extraction of this ion.

In addition, Onghena et al. (Ind. Eng. Chem.; 2015, 54, 1887-1898) describe the use of a biphasic aqueous bipyretic bis(trifluoromethylsulfonyl) imide betainium [Hbet][NTf₂]/NaCl system at different pH. The high viscosity of [Hbet][NTf₂] is detrimental to phase separation, which requires one hour. The use of this ionic liquid is complicated in that its hygroscopic character requires presaturation with water before use. In addition, the system does not allow efficient extractions at pHs below 1.5.

Alternative inexpensive compositions comprising an acidic aqueous solution that allows extraction and/or simple and effective separation of metal ions is therefore sought.

For this purpose, according to a first object, the invention relates to a composition comprising:

-   -   an ionic liquid of formula C⁺,(Xp−)_(1/p), in which:         -   C⁺ is an onium cation comprising at least one atom selected             from N, S, P or O, wherein the onium cation comprises at             least one hydrocarbon chain R¹ comprising from 6 to 20             carbon atoms, optionally interrupted by one or more groups             selected from among —S—, —O—, —(C═O)—O—, —O—(C═O)—,             —NR10-(C═O)—, —(C═O)—NR¹¹— or —NR¹²R¹³—, and/or optionally             substituted with one or more groups selected from halogen,             —OR¹⁴, —(C═O)R¹⁵, —(C═O)NR¹⁶R¹⁷—, —NR¹⁸R¹⁹R²⁰, —S—R²¹,             —(C═O)—OR²², wherein R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,             R¹⁸, R¹⁹, R²⁰, R²¹ and R²² independently represent H or a             linear or branched hydrocarbon chain comprising from 1 to 6             carbon atoms,         -   X^(p−) is an anion of charge p,

wherein the ionic liquid has a solubility in water at 20° C. of at least 10 g/L,

-   -   an acid, and     -   some water.

wherein the composition comprises two liquid phases:

-   -   a phase enriched in ionic liquid φ_(IL) and     -   a phase enriched in water φ_(W), whose pH is less than or equal         to 4.7.

The invention is based on the discovery that a biphasic aqueous system comprising an acidic aqueous phase may be obtained:

-   -   by using inexpensive and hydrophilic ionic liquids (solubility         in water at 20° C. of at least 10 g/L), and     -   without it being necessary to use a complex mixture of ions         (complex mixture of salts and/or acids) to obtain good phase         separation.

The composition according to the invention corresponds to a “biphasic aqueous liquid ionic/hydrophilic/inorganic salt system” in which the role of the organic salt is played by the acid. The composition according to the invention is a biphasic ionic-acidic aqueous system. It necessarily comprises two liquid phases φ_(IL) and φ_(W).

The fact that a composition comprising an acid, an ionic liquid and water, also comprises one or two liquid phases, depends on the nature and concentrations of the ionic liquid and the acid, the water concentration, and the temperature.

At a given temperature, the biphasic system is formed as soon as the concentrations of acid and ionic liquid are sufficient.

A composition comprising a given ionic liquid, a given acid, specific proportions of water, ionic liquid and acid, may be monophasic at certain temperatures and biphasic at other temperatures. The behavior of the composition may be of a lower critical solution temperature (LOST) type, i.e. that the composition is biphasic at temperatures above a certain temperature. Alternatively, the behavior of the composition may be of an upper critical solution temperature (UCST) solubility)type, i.e. that the composition is biphasic for temperatures below a certain temperature. Also, according to the alternative, raising or lowering the temperature promotes phase separation.

Generally, the composition according to the invention comprises two liquid phases φ_(IL) and φ_(W) at at least a temperature of between 0 and 100° C. In a first case, a composition comprising a given ionic liquid, a given acid, specific proportions of water, ionic liquid and acid may be biphasic at any temperature between 0 and 100° C. According to a second case, it may be monophasic between 0° C. and a given temperature T₁ and biphasic between the temperature T₁ and 100° C. (LOST). According to a third alternative, it may be biphasic between 0° C. and a given temperature T₂ and monophasic between the temperature T₂ and 100° C. (UCST). According to a fourth case, it may be monophasic between 0° C. and a given temperature T₃, biphasic between T₃ and a given temperature T₄ that is higher than T₃ and monophasic between the temperature T₄ and 100° C. The present case depends on the natures of the ionic liquid and the acid, their concentrations, and the concentration of water. Those skilled in the art know how to determine without difficulty and using a phase diagram whether a composition is biphasic at at least a temperature of between 0 and 100° C., and in what case defined above is the composition. It is therefore easy to prepare the composition according to the invention by mixing water, an acid and an ionic liquid in various proportions, preferably with the aid of a phase diagram.

The composition according to the invention comprises two liquid phases φ_(IL) and φ_(W). Each of these phases comprises water, acid and ionic liquid. However, the liquid phase φ_(IL) is enriched in ionic liquid, whereas the liquid phase φ_(W) is, by comparison, poor in ionic liquid and enriched in water. In other words, the molar proportion of ionic liquid [C⁺,(X^(p−))_(1/p)]φ_(IL) in the liquid phase φ_(IL) is greater than the molar proportion of ionic liquid [C⁺,(X^(p−))_(1/p)]φ_(W) in the liquid phase φ_(W), while the molar proportion of water [H₂O]φ_(IL) in the liquid phase φ_(IL) is less than the molar proportion of water [H₂O]φ_(W) in the liquid phase φ_(W).

The two liquid phases φ_(IL) and φ_(W) are visible to the naked eye. Typically, it is estimated that a composition comprises two liquid phases φ_(IL) and φ_(W) when its nephelometric turbidity unit (NTU) measured by nephelometry is greater than 30, preferably 50, when the composition is stirred, for example at 50 rpm.

The composition according to the invention comprises an ionic liquid of formula [C⁺,(X^(p−))_(1/p).

C⁺ is an onium cation comprising at least one atom chosen from among N, S, P or O, preferably chosen from among:

-   -   ammonium, phosphonium, sulphonium and     -   the cations of a saturated, unsaturated or aromatic heterocycle         comprising from 4 to 9 atoms, of which at least one heteroatom         is chosen from among N, S or O,

wherein the onium cation comprises at least one hydrocarbon chain R¹ as defined above.

The cation of such a heterocycle is, in particular, a pyridinium, a pyrrolidinium, a pyrazolium, an imidazolium, a thiazolium or an ixazolium, preferably a pyridinium, an imidazolium or a thiazolium.

The ionic liquid has one of the following formulas:

in which:

-   -   R¹ is as defined above,     -   R², R³ and R⁴ independently represent a hydrocarbon chain         comprising from 1 to 20 carbon atoms, optionally interrupted by         one or more groups chosen from —S—, —O—, —(C═O)—O—, —O—(C═O)—,         —NR¹¹⁰—(C═O)—, —(C═O)—NR¹¹¹— or —NR¹¹²R¹¹³—, and/or optionally         substituted by one or more groups chosen from a halogen, —OR¹¹⁴,         —(C═O)R¹¹⁵, —(C═O)NR¹¹⁶R¹¹⁷—, —NR¹¹⁸R¹¹⁹R¹²⁰, s R¹²¹,         (C═O)—OR¹²², wherein R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵, R¹¹⁶,         R¹¹⁷, R¹¹⁸, R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² independently represent H         or a linear or branched hydrocarbon chain comprising from 1 to 6         carbon atoms, wherein two groups selected from R¹, R², R³ and R⁴         may be connected to form a ring,     -   X^(p−) is an anion of charge p.

Generally, the R¹ chain of the onium cation, in particular the onium cation of the formulas (I) to (V) above, represents: an alkyl, an alkenyl, an alkynyl, wherein the alkyl, alkenyl and alkynyl comprise from 6 to 20 carbon atoms and are linear, branched or cyclic, being optionally interrupted by one or more groups chosen from —S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR¹⁰—(C═O)—, —(C═O)—NR¹¹— or —NR¹²R¹³—, and/or optionally substituted with one or more groups selected from a halogen, —OR¹⁴, —(C═O)R¹⁵, —(C═O)R¹⁶R¹⁷—, —NR¹⁸R¹⁹R²⁰, —S—R²¹, —(C═O)—OR²², where R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are as defined above, or an aryl comprising from 6 to 20 carbon atoms, wherein the aryl optionally comprises one or more atoms chosen from —S—, —O—, and —NR¹²R¹³—, and/or the aryl is optionally substituted by one or more groups chosen from halogen, —OR¹⁴, —(C═O)R¹⁵, —(C═O)NR¹⁶R¹⁷—, —R¹⁸R¹⁹R²⁰, —S—R²¹, —(C═O)—OR²², wherein R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are as defined above.

Preferably, the R¹ chain of the onium cation, in particular the onium cation of formulas (I) to (V) above, represents:

-   -   a linear, branched or cyclic alkyl comprising from 6 to 20         carbon atoms,     -   a linear, branched or cyclic alkoxyl containing from 6 to 20         carbon atoms, or a group of formula —[(CH₂)₂—O]_(x)—R¹⁵⁰, where         x represents an integer of 3 to 10 and R¹⁵⁰ represents H or a         linear or branched hydrocarbon-based chain containing from 1 to         6 carbon atoms, preferably a methyl,     -   a group of formula —[(CH₂)₃—O]—R¹⁵¹, where y represents an         integer from 2 to 6 and R¹⁵¹ represents H or a linear or         branched hydrocarbon-based chain containing from 1 to 6 carbon         atoms, preferably a methyl.

Preferably, the chain R¹ comprises at least 8, in particular at least 10, typically at least 12, for example at least 14 carbon atoms.

R²² generally represents a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms.

Preferably, the cation C⁺ comprises, in addition to the hydrocarbon chain R¹ defined above, a hydrocarbon chain R² comprising from 2 to 20 carbon atoms, in particular from 4 to 20 carbon atoms optionally interrupted by one or more groups chosen from among-S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR²¹⁰—(C═O)—, —(C═O)—NR²¹¹— or —NR²¹²R²¹³—, and/or optionally substituted by one or more groups selected from halogen, —OR²¹⁴, —(C═O)R²¹⁵, —(C═O)NR²¹⁶R²¹⁷—, —NR²¹⁸R²¹⁹R²²⁰, —S—R²²¹, (C═O)—OR²²², wherein R²¹⁰, R²¹¹, R²¹², R²¹³, R²¹⁴, R²¹⁵, R²¹⁶, R²¹⁷, R²¹⁸, R²¹⁹, R²²⁰, R²²¹ and R²²² independently represent H or a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, wherein the groups R¹ and R² may be connected to form a ring. This cation typically has one of the formulas (I), (II), (III), (IV) or (V) as defined above.

The C⁺ cation may comprise, in addition to the hydrocarbon chain R¹ and the hydrocarbon chain R² defined above, a hydrocarbon chain R³ comprising from 2 to 20 carbon atoms, especially from 4 to 20 carbon atoms, optionally interrupted by one or more groups selected from among —S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR³¹⁰—(C═O)—, —(C═O)—NR³¹¹— or —NR³¹²R³¹³—, and/or optionally substituted with one or more groups selected from among a halogen, —OR³¹⁴, —(C═O)R³¹⁵, —(C═O)NR³¹⁶R³¹⁷—, —NR³¹⁵R³¹⁹R³²⁰, —S—R³²¹, —(C═O)—OR³²², wherein R³¹⁰, R³¹¹, R³¹², R³¹³, R³¹⁴, R³¹⁵, R³¹⁶, R³¹⁷, R³¹⁸, R³¹⁹, R³²⁰, R³²¹ and R³²² independently represent H or a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, wherein two groups selected from R¹, R² and R³ may be connected to form a ring. This cation typically has one of the formulas (I), (IV) or (V) as defined above.

Preferably, R², R³ and R⁴ independently represent:

-   -   a linear, branched or cyclic alkyl comprising from 2 to 20         carbon atoms,     -   a linear, branched or cyclic alkoxyl containing from 2 to 20         carbon atoms, or a group of formula [(CH₂)₂—O]_(x′)—R¹⁵⁰,         wherein x′ represents an integer from 1 to 10 and R¹⁵⁰         represents H or a linear or branched hydrocarbon chain         containing from 1 to 6 carbon atoms, preferably a methyl,     -   a group of formula [(CH₂)₃—O]_(y′)—R¹⁵¹, wherein y′ represents         an integer from 1 to 6 and R¹⁵¹ represents H or a linear or         branched hydrocarbon chain containing from 1 to 6 carbon atoms,         preferably methyl.

Among the preferred ionic liquids, mention may be made of those of the following formulas (X), (XI), (XII), (XIII) or (XIV):

in which X^(p−) is an anion of charge p.

Preferably, in the composition according to the invention, the C⁺ cation does not comprise a negative charge. It is not a zwiterrion.

The anion X^(p−) is chosen especially from among the anions BF₄ ⁻, PF₆ ⁻, CF₃SO₃ ⁻, HSO₄ ⁻, SO₄ ²⁻, NO₃ ⁻, CH₃COO⁻, CF₃CO₂ ⁻, ClO₄ ⁻, HPO₄ ²⁻, H₂PO₄ ⁻, the halides (such as Cl⁻, Br⁻, I⁻ or F⁻), the anions BR⁵ ₄ ⁻, RCO₂ ⁻ or R⁵SO₃ ⁺, wherein X^(p−) is a linear or branched alkyl group comprising 1 to 4 carbon atoms, preferably a methyl. Preferably, X^(p−) is selected from halide anions, HSO₄ ⁻, SO₄ ²⁻, NO₃ ⁻, MeSO₃ ⁻. These anions are therefore “simple”, inexpensive, and not very toxic, unlike perfluorinated hydrophobic anions that are usually used to prepare ionic liquids immiscible in water. In addition, the ionic liquids comprising these “simple” anions are generally much less viscous than those prepared from perfluorinated hydrophobic anion. They are therefore easier to handle.

Preferably, in the composition according to the invention, the anion X^(p−) does not comprise a positive charge. It is not a zwiterrion.

The ionic liquid has a solubility in water at 20° C. of at least 10 g/L, preferably at least 20 g/L. The water used to measure this solubility is typically distilled water, for example milli-Q™ water. For example, the ionic liquid of formula (XI) above is soluble at 20° C. in any proportion. Those skilled in the art may very easily select ionic liquids having such solubilities in water.

Generally, the proportion of ionic liquid is 10 to 90% by weight in the composition.

The composition according to the invention comprises an acid. This acid allows the water-enriched phase φ_(W) to have a pH less than or equal to 4.7. The pH of the water-enriched phase φ_(W) is in particular less than 4.0, typically less than 3.0, or even less than 2.0, preferably less than 1.5, particularly preferably less than 1.0, for example less than 0.5, especially less than 0.2.

Generally, the acid is an acid of which at least one of the pKa is less than or equal to 4.7. When an acid has a single pKa, it is less than or equal to 4.7. When an acid has several pKa, it suffices that one of them is less than or equal to 4.7. The pKa is that measured in water at 25° C.

The acid may be organic, inorganic or a mixture thereof.

Among the organic acids, mention may be made of formic acid (pKa=3.8), acetic acid (pKa=4.7), oxalic acid (pKa=1.2) and lactic acid (pKa=3.9), uric acid (pKa=−1.1), p-toluenesulfonic acid (pKa=−2.8), trifluoromethanesulfonic acid (pKa=−12).

Among the inorganic acids, mention may be made of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or perchloric acid.

Preferably, the acid has the formula H_(p)(X^(p−)), where X^(p−) is the anion of the ionic liquid of the composition. The separation of the phases φ_(IL) and φ_(W) is then generally facilitated. For example:

-   -   the acid is hydrochloric acid and X^(p−) represents C^(l−),     -   the acid is sulfuric acid and X^(p−) represents HSO₄ ⁻ and/or         SO₄ ²⁻,     -   the acid is nitric acid and X^(p−) represents NO₃ ⁻,     -   the acid is phosphoric acid and X^(p−) represents H₂PO₄ ⁻, HPO₄         ²⁻ or PO₄ ³⁻, or     -   the acid is trifluoromethanesulphonic acid, and X^(p−)         represents CF₃SO₃ ⁻.

Preferably, the composition according to the invention comprises only one acid. In fact, it is not necessary to add a second acid to cause the phases φ_(IL) and φ_(W) to separate.

Generally, the concentration of acid in the composition is greater than or equal to 0.1 mol/l, especially greater than or equal to 1.5 mol/l, preferably greater than or equal to 1.0 mol/l.

The composition does not generally comprise additional ionic compounds to the ionic liquid, the acid and the metal ion salts (optionally in the form of complexes). In particular, the addition of additional ionic compounds is not necessary to cause the phases φ_(IL) and φ_(W) to separate. The composition according to the invention is therefore simple and inexpensive.

The composition according to the invention comprises water.

The composition generally comprises less than 5% by weight of organic solvent. It is preferably free of it.

The composition generally comprises less than 5% by weight of extracting agent (cyanide salt, ammonium, cyanex, crown ether, tributyl phosphate, for example). It is preferably free of it.

Generally, the cumulative proportions of the ionic liquid, water and acid are greater than 70% by weight, especially greater than 80% by weight, typically greater than 90% by weight, or even greater than 95% by weight, sometimes even greater than 99% by weight relative to the total weight of the composition.

The composition according to the invention is particularly useful for extracting a metal ion from an acidic aqueous medium comprising a metal ion, for separating metal ions from an aqueous medium comprising at least two metal ions, or for purifying an aqueous acidic solution comprising a metal ion.

For the purposes of the application, the term “metal ion” is intended to mean both the metal ion in free form (for example Co²⁺), the metal ion in the form of a complex with other ions (for example [Co(II)Cl₄]²⁻), the metal ion in hydrated form or not (for example [Co(H₂O)₅]²⁺), or in complexed and hydrated form. In the methods described below, the metal ion may be in one form at a certain stage and in another form at another stage.

The metal ions are generally soluble in acidic aqueous solutions. Advantageously, the composition according to the invention makes it possible to extract one or more metal ions in the liquid phase enriched in φ_(IL) ionic liquid.

The use of the composition according to the invention advantageously makes it possible to avoid the use of organic solvents such as kerosene.

The metal ion (M, M₁ or M₂ below) is preferably a metal ion capable of forming a negatively charged complex in the acidic aqueous phase φW. It is generally chosen from the ions of precious metals (gold, silver, platinum, rhodium and palladium), platinoids, refractory metals and rare earths.

Also, according to a second object, the invention relates to a method for extracting a metal ion M from a medium, comprising the steps of:

-   -   a) contacting an ionic liquid as defined above with an aqueous         medium comprising a metal ion M and an acid as defined above,         wherein a composition is obtained at a temperature Ti, and         wherein the composition comprises:         -   either a single liquid phase,         -   or two liquid phases φ_(IL) and φ_(W) (it is then a             composition according to the invention), provided that, at             the temperature T_(i), the partition coefficient of the             metal ion between the two phases φ_(IL) and φ_(W):

K(M)_(Ti)=[M]φ_(IL)/[M]φ_(W)

in which [M]φ_(IL) is the concentration of M in the phase φ_(IL) at the temperature T_(i) and [M]φ_(W) is the concentration of M in the phase φ_(W) at the temperature T_(i), is greater than 1, preferably greater than 1.1, in particular, greater than 2, even greater than 5, especially greater than 10, typically greater than 100,

-   -   b) when a composition comprising a single liquid phase is         obtained in step a), varying the temperature to obtain a         composition according to the invention at a temperature T_(f)         different from T_(i) comprising two liquid phases φ_(IL) and         φ_(W), provided that at the temperature T_(f), the partition         coefficient of the metal ion between the two phases φ_(IL) and         φ_(W):

K(M)_(Tf)=[M]φ_(IL)/[M]φ_(W)

in which [M]φ_(IL) is the concentration in M in the phase φ_(IL) at the temperature T_(f) and [M]φ_(W) is the concentration in M in the phase φ_(W) at the temperature T_(f), is greater than 1, preferably greater than 1.1, especially greater than 2, even greater than 5, especially greater than 10, typically greater than 100,

-   -   d) separating the phases φ_(IL) and φ_(W) of the composition         according to the invention obtained in step a) or b), then     -   e) optionally extracting the metal ion M from the phase φ_(IL).

The method is step-free b) when a composition comprising two liquid phases φ_(IL) and φ_(W) is obtained at the end of step a).

During step a) or b), the metal ion M is extracted in the φ_(IL) phase.

The aqueous medium of step a) is generally an aqueous solution.

It is advantageous for step a) to lead to a composition comprising only a single liquid phase (monophasic composition), in particular by choosing the temperature T_(i) in this sense. In fact, the thermotropic behavior of the composition (variation of the formation of two phases as a function of temperature) allows a rapid formation of the two phases during step b) and an immediate extraction of the metal ion during step b). When the composition is of the LOST type, it is necessary to increase the temperature to induce phase separation and T_(f) is greater than T_(i). When the composition is of the UCST type, it is necessary to reduce the temperature to induce the phase separation and T_(f) is lower than T_(i).

When step a) leads to a composition comprising two liquid phases φ_(IL) and φ_(W), it may be necessary to stir the two phases in order to obtain a good extraction of the metal ion M.

Of course, steps a), b) and c) may be repeated one or more times, which allows for several separation cycles. In this case, the φ_(W) phase obtained at the end of step c) may serve as an aqueous medium in step a) which is repeated.

The extraction process according to the invention may make it possible to recycle the metal ion.

The method may comprise, before step a), a step a_(o)) to prepare the aqueous medium comprising a metal ion M and an acid, typically by contacting an acidic aqueous solution with a medium comprising a metal ion M. This medium comprising a metal ion M may be an ore, a residue obtained after a chemical reaction or an electrolyte . . . . Step a₀) may be, for example, a leaching. The aqueous medium used in step a) is typically an acid leachate solution, as used in conventional hydrometallurgical processes. The extraction method according to the invention may be implemented in the context of a hydrometallurgical method.

By way of example, in the extraction method defined above, the ionic liquid has the formula (IV), preferably the formula (XI), the acid is HCl, and the metal ion M is Fe(III), Co(II) or Pt(IV).

The extraction yield of the extraction process according to the invention is advantageously extremely high, and generally higher than the usual yields obtained by carrying out extractions with organic solvents and extraction agents.

According to one embodiment, the aqueous medium comprising a metal ion M and an acid used in step a) comprises at least two different metal ions M₁ and M₂. The method may then be a method for separating the metal ions M₁ and M₂. According to a first alternative, the method is a method for separating metal ions M₁ and M₂ comprising the steps of:

-   -   a′) contacting an ionic liquid as defined above with an aqueous         medium comprising two metal ions M₁ and M₂ (of different         natures) and an acid as defined above, wherein a composition is         obtained at a temperature T_(i), and the composition comprises:         -   either a single liquid phase,         -   or two liquid phases φ_(IL) and φ_(W), provided that, at the             temperature T_(i), the separation factor β(M₁/M₂)_(Ti),             corresponds to the ratio between the partition coefficients             of M₁ and M₂

β(M ₁ /M ₂)_(Ti) =K(M ₁)_(Ti) /K(M ₂)_(Ti)=([M ₁]φ_(IL)/[M ₁]φ_(W))/([M ₁]φ_(IL)/[M ₁]φ_(W))

-   -   in which:         -   K(M₂)_(Ti) is the partition coefficient at the temperature             T_(i) of the metal ion M₁ between the two phases φ_(IL) and             φ_(W), with K(M₁)_(Ti)=[M]φ_(IL)/[M₁]φ_(W),         -   K(M₂)_(Ti) is the partition coefficient at the temperature             T_(i) of the metal ion M₂ between the two phases φ_(IL) and             φ_(W), with K(M₂)_(Ti)=[M₂]φ_(IL)/[M₂]φ_(W),         -   [M₁]_(φIL) is the concentration in M₁ in the phase φ_(IL) at             the temperature T_(i) and [M₁]φ_(W) is the concentration in             M₁ in the phase φ_(W) at the temperature         -   [M₂]_(φIL) is the concentration in M₂ in the phase φ_(IL) at             the temperature T_(i) and [M₂]φ_(W) is the concentration in             M₂ in the phase φ_(W) at the temperature T_(i), is greater             than 1, preferably greater than 1.1, especially greater than             2, or even greater than 5, especially greater than 10,             typically greater than 100.     -   b′) when a composition comprising a single liquid phase is         obtained in step a′), varying the temperature to obtain a         composition according to the invention at a temperature T_(f)         different from T_(i) comprising two liquid phases φ_(IL) and         φ_(W), under reserves that, at the temperature T_(f), the         separation factor b(M₁/M₂)_(Tf) corresponding to the ratio         between the partition coefficients of M₁ and M₂

b(M ₁ /M ₂)_(Tf) =K(M ₁)_(Ti) /K(M ₂)_(Tf)=([M ₁]φ_(IL)/[M ₁]φ_(W))/([M ₁]φ_(IL)/[M ₁]φ_(W))

-   -   in which:         -   K(M₁)_(Ti) is the partition coefficient at the temperature             T_(f) of the metal ion M₁ between the two phases φ_(IL) and             φ_(W), with K(M₁)_(Tf)=[M₁]φ_(IL)/[M₁]φ_(W),         -   K(M₂)_(Tf) is the partition coefficient at the temperature             T_(f) of the metal ion M₂ between the two phases φ_(IL) and             φ_(W), with K(M₂)_(Tf)=[M₂]φ_(IL)/[M₂]φ_(W)         -   [M₁]_(φIL) is the concentration in M₁ in the phase φ_(IL) at             the temperature T_(f) and [M₂]φ_(W) is the concentration in             M₁ in the phase φ_(W) at the temperature T_(f),         -   [M₂]_(φIL) is the concentration in M₂ in the phase φ_(IL) at             the temperature T_(f) and [M₂]φ_(W) is the concentration in             M₂ in the phase φ_(W) at the temperature T_(f), is greater             than 1, preferably greater than 1.1, especially greater than             2, even greater than 5, especially greater than 10,             typically greater than 100,     -   c′) separating the phases φ_(IL) and φ_(W) of the composition         according to the invention obtained in step a′) or b′), then     -   d) optionally extracting the metal ion M₁ from the phase φ_(IL),     -   e′) optionally extracting the metal ion M₂ from the phase φ_(W).

This embodiment advantageously makes it possible to separate at least two metal ions M₁ and M₂. During step a′) or b′), the metal ion M₁ is extracted in the phase φ_(IL) while the metal ion M₂ remains in the phase φ_(W).

By way of example, in the extraction method according to the first alternative defined above, the ionic liquid has the formula (IV), preferably the formula (XI), the acid is HCl, and the metal ion M₁ is Co(II) and the metal ion M₂ is Ni(II). Cobalt and nickel are two neighboring metals in the periodic table. In addition, they are often associated both in the ores that produce these metals in the devices to recycle. Methods able to separate them easily are therefore sought.

Of course, steps a′), b′) and c′) may be repeated one or more times, which allows for several separation cycles. In this case, the phase φ_(W) obtained at the end of step c′) serves as an aqueous medium in step a′) which is repeated.

According to a second alternative, the method is a method for separating metal ions M₁ and M₂ comprising the steps of:

-   -   a″) contacting an ionic liquid as defined above with an aqueous         medium comprising an acid as defined above and two metal ions M₁         and M₂ (of different natures), wherein a composition with a         temperature T_(i), and wherein the composition comprises:         -   either a single liquid phase,         -   or two liquid phases φ_(IL) and φ_(W), provided that, at the             temperature T_(i):             -   the partition coefficient of the metal ion M₁ between                 the two phases φ_(IL) and φ_(W):

K(M ₁)_(Ti)=[M ₁]φ_(IL)/[M ₁]φ_(W)

-   -   -   -   is greater than 1, preferably greater than 1.1,                 especially greater than 2, even greater than 5,                 especially greater than 10, typically greater than 100,             -   the partition coefficient of the metal ion M₂ between                 the two phases φ_(IL) and φ_(W):

K(M ₁)_(Tf)=[M ₁]φ_(IL)/[M ₁]φ_(W)

-   -   -   -   is greater than 1, preferably greater than 1.1,                 especially greater than 2, even greater than 5,                 especially greater than 10, typically greater than 100,

    -   b″) when a composition comprising a single liquid phase is         obtained in step a″), varying the temperature to obtain a         composition according to the invention at a temperature T_(f)         different from T_(i) comprising two liquid phases φ_(IL) and         φ_(W) provided that at temperature T_(f):         -   the partition coefficient of the metal ion M₁ between the             two phases φ_(IL) and φ_(W):

K(M ₁)_(Tf)=[M ₁]φ_(IL)/[M ₁]φ_(W)

-   -   is greater than 1, preferably greater than 1.1, especially         greater than 2, even greater than 5, especially greater than 10,         typically greater than 100,         -   the partition coefficient of the metal ion M₂ between the             two phases φ_(IL) and φ_(W):

K(M ₂)_(Tf)=[M ₂]φ_(IL)/[M ₂]φ_(W)

-   -   is greater than 1, preferably greater than 1.1, especially         greater than 2, even greater than 5, especially greater than 10,         typically greater than 100,     -   c″) separating the phases φ_(IL) and φ_(W) of the composition         according to the invention obtained in step a″) or b″), then     -   d″) contacting, at a temperature T_(Ω), the φ_(IL) phase with an         aqueous solution such that:         -   the solubility in the aqueous solution at the temperature             T_(Ω) of M₁ is greater than or equal to 0.01 mol/l,         -   the solubility in the aqueous solution at the temperature             T_(Ω) of M₂ is less than or equal to 0.001 mol/l,     -   wherein M₂ precipitates and a medium Ω comprising a solid         comprising M₂ and at least one liquid phase comprising M₁ is         obtained,     -   e″) optionally filtering the medium Ω to recover the solid         comprising M₂,     -   f″) optionally extracting the metal ion M₁ from the liquid         phase. The medium Ω may comprise one or two liquid phases.

During step a″) or b″), the metal ions M₁ and M₂ are extracted in the phase φ_(IL). It is the addition of the aqueous phase during step d″) which makes it possible to separate the two metal ions, since the metal ion M₁ remains in the liquid phase (mixture of ionic liquid, aqueous phase and the metal ion M₁) while the metal ion M₂ precipitates. The separation is therefore induced taking into account differences in the solubilities of M₁ and M₂ in the aqueous solution introduced in step d″).

Of course, the steps a″, b″) and c″) may be repeated one or more times, which allows for several separation cycles. In this case, the φ_(W) phase obtained at the end of step c″) serves as an aqueous medium in step a″) which is repeated.

By way of example, in the extraction method according to the second alternative defined above, the ionic liquid has the formula (IV), preferably the formula (XI), the acid is HCl, and the metal ion M₁ is Co(II), and the metal ion M₂ is Pt(IV). Typically, the aqueous medium comprising an acid used in step a″) is an aqueous solution of pH less than −0.5, for example an aqueous solution of 10M HCl (in which the Pt(IV) ions are soluble) and the aqueous solution implemented in step d) is an aqueous solution of pH greater than 0.5, for example an aqueous solution of 1M HCl (in which the Pt(IV) ions are not soluble).

According to a third object, the invention relates to a method for purifying an acidic aqueous solution comprising a metal ion M comprising the steps of:

-   -   i) contacting an ionic liquid as defined above with an aqueous         solution S comprising a metal ion M at a [M]_(S) concentration         and an acid as defined above, wherein a composition at a         concentration of temperature T_(i) is obtained, and wherein the         composition comprises:         -   either a single liquid phase,         -   or two liquid phases φ_(IL) and φ_(W), provided that, at the             temperature T_(i), the partition coefficient of the metal             ion between the two phases φ_(IL) and φ_(W):

K(M)_(Ti)=[M]φ_(IL)/[M]φ_(W)

-   -   is greater than 1, preferably greater than 1.1, especially         greater than 2, even greater than 5, especially greater than 10,         typically greater than 100,     -   ii) when a composition comprising a single liquid phase is         obtained in step i), varying the temperature to obtain a         composition according to the invention at a temperature T_(f)         different from T_(i) comprising two liquid phases φ_(IL) and         φ_(W), provided that at the temperature T_(f), the partition         coefficient of the metal ion between the two phases φ_(IL) and         φ_(W):

K(M)_(Tf)=[M]φ_(IL)/[M]φ_(W)

-   -   is greater than 1, preferably greater than 1.1, especially         greater than 2, even greater than 5, especially greater than 10,         typically greater than 100,     -   iii) separating the phases φ_(IL) and φ_(W) of the composition         according to the invention obtained in step i) or ii), wherein a         phase φ_(W) is obtained which is an acidic aqueous solution         whose concentration of metal ion M [M]φ_(W) is less than the         concentration [M]_(S).

Of course, steps i), ii) and iii) may be repeated one or more times, which allows for several separation cycles. In this case, the φ_(W) phase obtained at the end of step iii) serves as aqueous solution S in step i) which is repeated.

This method may be used to recycle the acidic aqueous solution.

The method may comprise, after step iii), a step iv) of extracting the metal ion M from the φ_(IL) phase.

The steps of extraction of the metal ion d), d′), e′), f″) and iv) defined above may be, for example, implemented:

-   -   by release of the metal ion in another phase,     -   by precipitation of the metal ion, wherein this precipitation is         capable of being induced by a complexing agent for the metal ion         to be extracted, for example oxalic acid, or     -   by electrochemistry.

The invention is illustrated in light of the figures and examples which follow, given by way of illustration.

FIGURES

FIG. 1 shows a phase diagram formed by ionic liquid [P₄₄₄₁₄][C1] and HCl at four different temperatures, namely 24° C., 36° C., 45° C. and 56° C. For each temperature, the biphasic system/monophasic system transition is represented as a function of the [P₄₄₄₁₄][Cl] mass concentration (ordinate) and the HCl mass concentration (abscissa).

FIG. 2 shows a diagram of the protocol followed in Example 3.

FIG. 3 shows a diagram of the protocol followed in Example 4.

EXAMPLE 1: BIPHASIC SYSTEM [P₄₄₄₁₄][CL]—HCL—H₂O

Compositions comprising water, HCl and tributyltetradecylphosphonium chloride [P₄₄₄₁₄][Cl] (Cytec Industries) were prepared by varying the mass concentrations of ionic liquid [P₄₄₄₁₄][Cl] and HCl at four temperatures (24° C., 36° C., 45° C. and 56° C.). Depending on the proportions and the temperatures, a monophasic or biphasic medium was obtained.

FIG. 1 shows a phase diagram for each of the temperatures tested.

The system is biphasic when the prepared mixture corresponds to a point located in the right zone of the curve shown in FIG. 1. The system then corresponds to a composition according to the invention.

On the other hand, since the mixture prepared corresponds to a point situated in the zone to the left of the curve presented in FIG. 1, the system is monophasic (a homogeneous phase) and these systems are therefore not compositions according to the invention.

At 45° C., the biphasic system is formed at lower HCl concentrations than those required at 25° C. This is characteristic of an LCST type behavior.

EXAMPLE 2: USE OF A BIPHASIC SYSTEM [P₄₄₄₁₄][CL]—HCL—H₂O TO EXTRACT FE(III) IONS

Iron has been used as an example of a metal whose presence in aqueous solution requires the use of acid to avoid the formation of iron hydroxide and the precipitation of the metal ion.

0.015 g of FeCl₃.6H₂O (supplied by Alfa Aesar) was dissolved in 50 mL at 10 M HCl (supplied by Roth). The solution was yellow. 1 ml of this solution was mixed with 0.25 g of [P₄₄₄₁₄][Cl] (supplied by Cytec) at 25° C. A biphasic composition was obtained, comprising:

-   -   a yellow upper phase: the phase enriched in ionic liquid φ_(IL)         comprising Fe(III), and     -   an almost colorless lower phase: the phase enriched in water         φ_(W).

The partition coefficient of the Fe(III) metal ion between the two phases φ_(IL) and φ_(W) was

K(Fe(III))_(n)=[Fe(III)]φ_(IL)/[Fe(III)]φ_(W)>750

Fe(III) was quantitatively extracted with acidic ABS [P₄₄₄₁₄][Cl]—HCl—H₂O. More than 99.7% of the Fe(III) is extracted from the acidic aqueous phase as measured by flame absorption spectroscopy.

EXAMPLE 3: USE OF A BIPHASIC SYSTEM [P₄₄₄₁₄][CL]—HCL—H₂O TO SEPARATE NI AND CO IONS

In 50 mL of an 18 wt % HCl aqueous solution, 0.065 g of NiCl₂ and 0.12 g of CoCl₂.6H₂O (supplied by Alfa Aesar) were mixed at 25° C. In 1 mL of this solution, 0.25 g of [P₄₄₄₁₄][Cl] was added. The mixture was monophasic at 25° C., blue in color. The mixture was heated to 50° C., which induced phase separation, namely:

-   -   a blue upper phase: the phase enriched in φ_(IL) ionic liquid         comprising cobalt (II), and     -   an almost colorless lower phase: the water-enriched phase φ_(W)         in which the nickel (II) remained.

The protocol followed is illustrated in FIG. 2. The analyzes were carried out by flame absorption spectroscopy.

The partition coefficient of the Co(II) metal ion between the two phases φ_(IL) and φ_(W) was

K(Co(II))_(Ti)=[Co(II)]φ_(IL)/[Co(II)]φ_(W)=190

The partition coefficient of the Fe(III) metal ion between the two phases φ_(IL) and φ_(W) was

K(Ni(II))_(Ti)=[Ni(II)]φ_(IL)/[Ni(II)]φ_(W)=0.14

A one-step and quantitative separation of cobalt and nickel was thus achieved, which is an advantage over the methods usually used in the prior art. The nickel-cobalt separation is not effective with conventional methods and requires several consecutive extraction steps to obtain a quantitative separation of the two metal ions.

EXAMPLE 4: USE OF A BIPHASIC SYSTEM [P₄₄₄₁₄][CL]—HCL—H₂O TO SEPARATE PT AND CO IONS

Platinum is known as a noble metal which dissolves only in very acid aqueous solutions (typically in aqua regia: a mixture of hydrochloric acid and nitric acid concentrated in a proportion of 2 to 4 volumes of hydrochloric acid for 1 volume of nitric acid.

To 1 mL of a 10M aqueous HCl solution comprising 0.005M Co (II) and 0.01M Pt(IV) added as H₂PtClO₆.3H₂O and CoCl_(2.6)H₂O (supplied by Alfa Aesar) at 25° C. were introduced 0.25 g of [P₄₄₄₁₄][Cl]. Without heating, a phase separation takes place, namely:

-   -   a green upper phase: the phase enriched in φ_(IL) ionic liquid         comprising cobalt (II) and platinum (IV), and     -   an almost colorless lower phase: the phase enriched in water         φ_(W).

The partition coefficient of the metal ion Pt(IV) between the two phases φ_(IL) and φ_(W) was

K(Pt(IV))_(Ti)=[Pt(IV)]φ_(IL)/[Pt(IV)]φ_(W)>100

[P₄₄₄₁₄][Cl]—HCl—H₂O thus made it possible to obtain a quantitative extraction of platinum and cobalt towards the phase rich in ionic liquid φ_(IL).

The two phases φ_(IL) and φ_(W) were separated. To the phase enriched in isolated φIL ionic liquid was added 1.5 ml of 1M aqueous HCl solution, which induced the precipitation of platinum (in the form of an insoluble salt of PtCl₆ ²⁻), since platinum is not soluble in an aqueous solution so little acidic. A mixture comprising:

-   -   a salt which precipitates at the bottom which consists of PtCl₆         ²⁻ and     -   a single liquid phase comprising water, cobalt, [P₄₄₄₁₄][Cl] and         HCl, was obtained.

The protocol followed is shown in FIG. 3. 

1-13. (canceled)
 14. Method for extracting a metal ion M from a medium, comprising the steps of: a) contacting an ionic liquid of formula C⁺,(X^(p−))_(1/p), in which: C⁺ is an onium cation comprising at least one atom selected from N, S, P or O, the onium cation comprising at least one hydrocarbon chain R¹ comprising from 6 to 20 carbon atoms, optionally interrupted by one or more groups selected from —S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR¹⁰—(C═O)—, —(C═O)—NR¹¹— or —NR¹²R¹³—, and/or optionally substituted with one or more groups selected from halogen, —OR¹⁴, —(C═O)R¹⁵, —(C═O) NR¹⁶R¹⁷—, —NR¹⁸R¹⁹R²⁰, —S—R²¹, —(C═O)—OR²², wherein R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ independently represent H or a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms and R²² represents a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, and X^(p−) is an anion charge of p, the ionic liquid having a solubility in water at 20° C. of at least 10 g/L, with an aqueous medium comprising a metal ion M and an acid, wherein a composition is obtained at a temperature T_(i), the composition comprising a single liquid phase, b) varying the temperature to obtain a composition at a temperature T_(f) different from T_(i) comprising two liquid phases φ_(IL) and φ_(W), the liquid phase φ_(IL) being a phase enriched in ionic liquid and the liquid phase φ_(W) being a phase enriched in water, the pH is less than or equal to 4.7, with the proviso that, at temperature T_(f), the partition coefficient of the metal ion between the two phases φ_(1L) and φ_(W): K(M)_(Tf)=[M]φ_(IL)/[M]φ_(W) in which [M]φ_(IL) is the concentration in M in the phase φ_(IL) at the temperature T_(f) and [M]φ_(W) is the concentration in M in the phase φ_(W) at the temperature T_(f), is greater than 1, preferably greater than 1.1, especially greater than 2, even greater than 5, especially greater than 10, typically greater than 100, c) separating the phases φ_(IL) and φ_(W) of the composition obtained in step b), then d) optionally extracting the metal ion M from the phase φ_(IL).
 15. Method for separating metal ions M₁ and M₂, comprising the steps of: a′) contacting an ionic liquid of formula C⁺,(X^(p−))_(1/p), in which: C⁺ is an onium cation comprising at least one atom selected from N, S, P or O, the onium cation comprising at least one hydrocarbon chain R¹ comprising from 6 to 20 carbon atoms, optionally interrupted by one or more groups selected from —S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR¹⁰—(C═O)—, —(C═O)—NR¹¹— or —NR¹²R¹³—, and/or optionally substituted with one or more groups selected from an halogen, —OR¹⁴, —(C═O)R¹⁵, —(C═O) NR¹⁶R¹⁷—, —NR¹⁸R¹⁹R²⁰, —S—R²¹—, —(C═O)—OR²², wherein R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ independently represent H or a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms and R²² represents a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, and X^(p−) is an anion of charge p, wherein the ionic liquid has a solubility in water at 20° C. of at least 10 g/L, with an aqueous medium comprising two metal ions M₁ and M₂ (of different natures) and an acid, wherein a composition is obtained at a temperature T_(i), and wherein the composition comprises a single liquid phase, b′) varying the temperature to obtain a composition at a temperature T_(f) different from T_(i) comprising two liquid phases φ_(IL) and φ_(W), the liquid phase φ_(IL) being a phase enriched in ionic liquid and the liquid phase φ_(W) being a phase enriched in water, of which the pH is less than or equal to 4.7, provided that, at the temperature T_(f), the separation factor b(M₁/M₂)_(Tf) corresponding to the ratio between the partition coefficients of M₁ and M₂ β ß(M ₁ /M ₂)_(Tf) =K(M ₁)_(Ti) /K(M ₂)_(Tf)=[M ₁]φ_(IL)/[M ₁]φ_(W))/([M ₁]φ_(IL)/[M ₁]φ_(W) in which: K(M₁)_(Ti) is the partition coefficient at the temperature T_(f) of the metal ion M₁ between the two phases φ_(IL) and φ_(W), with K (M₁)_(Tf)=[M₁]φ_(IL)/[M₁]φ_(W), K(M₁)_(Ti) is the partition coefficient at the temperature T_(f) of the metal ion M₂ between the two phases φ_(IL) and φ_(W), with K (M₂)_(Tf)=[M₂]φ_(IL)/[M₂]φ_(W) [M₁]_(φIL) is the concentration in M₁ in the phase φ_(IL) at the temperature T_(f) and [M₁]φ_(W) is the concentration in M₁ in the phase φ_(W) at the temperature T_(f), [M₂]_(φIL) is the concentration in M₂ in the phase φ_(IL) at the temperature T_(f) and [M₂]φ_(W) is the concentration in M₂ in the phase φ_(W) at the temperature T_(f), is greater than 1, preferably greater than 1.1, especially greater than 2, even greater than 5, especially greater than 10, typically greater than 100, c′) separating the phases φ_(IL) and φ_(W) of the composition obtained in step b′), then d′) optionally extracting the metal ion M₁ from the phase φ_(IL), e′) optionally extracting the metal ion M₂ from the phase φ_(W).
 16. Method for separating metal ions M₁ and M₂ comprising the steps of: a″) contacting an ionic liquid of formula C⁺,(X^(p−))_(1/p), wherein: C⁺ is an onium cation comprising at least one atom selected from N, S, P or O, the onium cation comprising at least one hydrocarbon chain R¹ comprising from 6 to 20 carbon atoms, optionally interrupted by one or more groups selected from —S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR¹⁰—(C═O)—, —(C═O)—NR¹¹— or —NR¹²R¹³—, and/or optionally substituted with one or more groups selected from a halogen, —OR¹⁴, —(C═O)R¹⁵, —(C═O)NR¹⁶R¹⁷—, —NR¹⁸R¹⁹R²⁰, —S—R²¹, —(C═O)—OR²², wherein R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ independently represent H or a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms and R²² represents a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, and X^(p−) is an anion of charge p, wherein the ionic liquid has a solubility in water at 20° C. of at least 10 g/L, with an aqueous medium comprising an acid and two metal ions M₁ and M₂ (of different natures), wherein a composition is obtained at a temperature T_(i), the composition comprising: either a single liquid phase, or two liquid phases φ_(IL) and φ_(W), the liquid phase φ_(IL) being a phase enriched in ionic liquid and the liquid phase φ_(W) being a phase enriched in water, whose pH is less than or equal to 4.7, provided that at temperature T_(i): the partition coefficient of the metal ion M₁ between the two phases φ_(IL) and φ_(W): K(M ₁)_(Ti)=[M ₁]φ_(IL)/[M ₁]φ_(W) is greater than 1, preferably greater than 1.1, especially greater than 2, even greater than 5, especially greater than 10, typically greater than 100, the partition coefficient of the metal ion M2 between o the two phases φIL and φW: K(M ₁)_(Ti)=[M ₁]φ_(IL)/[M ₁]φ_(W) is greater than 1, preferably greater than 1.1, especially greater than 2, even greater than 5, especially greater than 10, typically greater than 100, b″) when a composition comprising a single liquid phase is obtained in step a″), varying the temperature to obtain a composition at a temperature Tf different from Ti comprising two liquid phases φIL and φW, the liquid phase φIL being a phase enriched in ionic liquid and the liquid phase φW being a phase enriched in water, whose pH is less than or equal to 4.7, provided that at the temperature Tf: the partition coefficient of the metal ion M1 between the two phases φIL and φW: K(M ₁)_(Tf)=[M ₁]φ_(IL)/[M ₁]φ_(W) is greater than 1, preferably greater than 1.1, especially greater than 2, even greater than 5, especially greater than 10, typically greater than 100, the partition coefficient of the metal ion M₂ between the two phases φ_(IL) and φ_(W): K(M ₂)_(Tf)=[M ₂]φ_(IL)/[M ₂]φ_(W) is greater than 1, preferably greater than 1.1, especially greater than 2, even greater than 5, especially greater than 10, typically greater than 100, c″) to separate the phases φ_(IL) and φ_(W) of the composition obtained in step a″) or b″), then d″) contacting, at a temperature T_(Ω), the φ_(IL) phase with an aqueous solution such that: the solubility in the aqueous solution at the temperature T_(Ω) of M₁ is greater than or equal to 0.01 mol/l, the solubility in the aqueous solution at the temperature T_(Ω) of M₂ is less than or equal to 0.001 mol/l, wherein M₂ precipitates and a medium Ω comprising a solid comprising M₂ and at least one liquid phase comprising M₁ is obtained, e″) optionally filtering the medium Ω to recover the solid comprising M₂, f″) optionally extracting the metal ion M₁ from the liquid phase.
 17. Method for purifying an acidic aqueous solution comprising a metal ion M comprising the steps of: i) contacting an ionic liquid of formula C⁺,(X^(p−))_(1/p), in which: C⁺ is an onium cation comprising at least one atom selected from N, S, P or O, the onium cation comprising at least one hydrocarbon chain R¹ comprising from 6 to 20 carbon atoms, optionally interrupted by one or more groups selected from —S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR¹⁰—(C═O)—, —(C═O)—NR¹¹— or —NR¹²R¹³—, and/or optionally substituted with one or more groups selected from halogen, —OR¹⁴, —(C═O) R¹⁵, —(C═O) NR¹⁶R¹⁷—, —NR¹⁸R¹⁹R²⁰, —S—R²¹, —(C═O)—R²², wherein R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ independently represent H or a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms and R²² represents a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, and X^(p−) is an anion of charge p, the ionic liquid having a solubility in water at 20° C. of at least 10 g/L, with an aqueous solution S comprising a metal ion M at a [M]_(S) concentration and an acid, wherein a composition is obtained at a temperature T_(i), the composition comprising a single liquid phase, ii) varying the temperature to obtain a composition at a temperature T_(f) different from T_(i) comprising two liquid phases φ_(IL) and φ_(W), the liquid phase φ_(IL) being a phase enriched in ionic liquid and the liquid phase φ_(W) being a phase enriched in water, the pH is less than or equal to 4.7, provided that, at the temperature T_(f), the partition coefficient of the metal ion between the two phases φ_(IL) and φ_(W): K(M)_(Tf)=[M]φ_(IL)/[M]φ_(W) is greater than 1, preferably greater than 1.1, especially greater than 2, even greater than 5, especially greater than 10, typically greater than 100, iii) separating the phases φ_(IL) and φ_(W) of the composition obtained in stage ii), wherein a phase φ_(W) is obtained which is an acidic aqueous solution whose concentration of metal ion M[M]φ_(W) is lower than the concentration [M]_(S).
 18. Method according to claim 14, comprising before step a), a step a₀) of preparing the aqueous medium comprising a metal ion M and an acid by leaching.
 19. Method according to claim 14, wherein the ionic liquid has one of the following formulas:

in which: R¹ and X^(p−) are as defined in claim 14, R², R³ and R⁴ independently represent a hydrocarbon chain comprising from 1 to 20 carbon atoms, optionally interrupted by one or more groups chosen from —S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR¹¹⁰—(C═O)—, —(C═O)—NR¹¹¹— or —NR¹¹²R¹¹³—, and/or optionally substituted by one or more groups chosen from a halogen, —OR¹¹⁴, —(C═O)R¹¹⁵, —(C═O)NR¹¹⁶R¹¹⁷—, —R¹¹⁸R¹¹⁹R¹²⁰, —S—R¹²¹, —(C═O)—OR¹²² wherein R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵, R¹¹⁶, R¹¹⁷, R¹¹⁸, R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² independently represent H or a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, wherein two groups selected from R¹, R², R³ and R⁴ may be connected to form a ring.
 20. Method according to claim 19 wherein the R¹ chain comprises at least 8, especially at least 10, typically at least 12, for example at least 14 carbon atoms.
 21. Method according to claim 18, wherein the C⁺ cation comprises, in addition to the hydrocarbon chain R¹, a hydrocarbon chain R² comprising from 2 to 20 carbon atoms, in particular from 4 to 20 carbon atoms optionally interrupted by one or more groups selected from —S—, —O—, —(C═O)—O—, —O—(C═O)—, —NR²¹⁰—(C═O)—, —(C═O)—NR²¹¹— or —NR²¹²R²¹³—, and/or optionally substituted with one or more groups selected from halogen, —OR²¹⁴, —(C═O)R²¹⁵, —(C═O)NR²¹⁶R²¹⁷—, —NR²¹⁸R²¹⁹R²²⁰, —S—R²²¹, —(C═O)—OR²²², wherein R²¹⁰, R²¹¹, R²¹², R²¹³, R²¹⁴, R²¹⁵, R²¹⁶, R²¹⁷, R²¹⁸, R²¹⁹, R²²⁰, R²²¹ and R²²² independently represent H or a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms, wherein the groups R¹ and R² may be connected to form a ring.
 22. Method according to claim 19, wherein the ionic liquid has one of the following formulas

in which X^(p−) is an anion of charge p.
 23. Method according to claim 19, wherein the anion X^(p−) is selected from anions BF₄ ⁻, PF₆ ⁻, CF₃SO₃ ⁻, HSO₄ ⁻, SO₄ ²⁻, NO₃ ⁻, CH₃COO⁻, CF₃CO₂ ⁻, ClO₄ ⁻, HPO₄ ²⁻, H₂PO₄ ⁻, halides, anions BR⁵ ₄ ⁻, RCO₂ ⁻ or R⁵SO₃ ⁻, R⁵ being a linear or branched alkyl group having from 1 to 4 carbon atoms, preferably methyl.
 24. Method according to claim 14, wherein the pH of the water-enriched phase 0 is less than 4.0, typically less than 3.0, or even less than 2.0, preferably less than at 1.5, particularly preferably less than 1.0, for example less than 0.5, especially less than 0.2.
 25. Method according to claim 14, wherein the acid is: an organic acid chosen from formic acid, acetic acid, oxalic acid, lactic acid, uric acid, p-toluenesulphonic acid, trifluoromethanesulphonic acid or a mixture thereof, an inorganic acid chosen from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or a mixture thereof, or a mixture thereof.
 26. Method according to claim 14, wherein the acid has the formula H_(p)(X^(p−)), where is X^(p−) is the anion of charge p of the ionic liquid of the composition. 